Azo dyestuffs from 2.3-hydroxynaphthoic acid arylids and process of making the same



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LEOPOLID LASKA ASSZGNORS T9 GEM EAL REEL TIZON 0F DELAY/ARE No Drawing. Application filed IEay 22,

The present invention relates to new azo dyestuffs from 2.3-l1YClIOX -llaPllbllQlC acid arylids and a process of pre iaring' the s n- We have found that vahiable novel azo stills are obtained it 2.3-liyoroxyna acid ar tlids are allowed to couple with the diazo compounds obtained from amines oi the general type:

lO.Nl-l.ar \'l wherein :0 represents a- Lelogen atom or an allzyl group.

The most probable graphical representation for our novel dyestuffs is the formula:

I GO.NH.ary1

wherein represents a halogen atom or c .l kyl group. These (,OlOliilfl matters are ii ry state reddish to dark colored powders, which dissolve in concentrated suli'uric aciC \x'it' from blue to dark violet colors. re-

ducuion the original amines or o re a'lioresaid re recovered toge her with l-annno-Q- napl ,iie-l-cai=bo:qvlic (.Cld aryihe new dyestuffs may be produced either as such or on a base, i. e.. on sub t=. an or on the vegetable fibre. or pre- Mixed \Vleli cipitate-d on substrates these novel dyestulis produce valuable color lake tbc-rinoi'e of great interest in the dyeing of veo etaole fibres. The dve 'Q is in this case e, the dyeings directly produced on the r and obtained are of exceediin lear shades particularly fast to kier Joilin A The amines of the afore a prepzred by causing chl orb res further subsz ed manner besides react on primary or secon .l

AND AETEI F, .J' R ICI in Germany May 28, 1925.

may contain further sub resiclne,z1nc by reducing h 'troconipounds obtained, or e obtained by ction of a. condensing a 'ent, such as phossoituents in an aryl L c 11 .hey may b hlorire .1 iXture of a ni- '1) ylic acid srbs'titutcd as above nesc'iber; vitL an eventually substituted pri- 1 oncary aniinobase, adva itageousmarry or see ly in a dil or solvent, and by a subse- L 1 o quent reduction.

The following examples will further illustrate our novel process and the products obtained by it. We Wish it however to be understoofL that We. are not limited to the particular conditions nor to the specific products mentioned therein. The parts are by Weight.

4.8 ar r ciloi'o-aniline are thoroughly stirred up with 14. parts of lYCllO-SllOllC acid (spec. gray.

ater and ice are add d parts of sec d obtained in the form of a brilliant l'Qi". paste. When mixed Wih the substrate. 5 iorins valuable bluish red usual Likes. iL'EtQl ';1n,; 1C dissolves in concentrated sulfuric acid Witl a bluish Wine red c or and has most probably the formula:

Ewample 2 d driec arn is impreg- V Clltfllllllg per liter 3 h phthoy -,l-3-naphthyltic soda and S CC. Oi C(ZUE v -2 saline. 3

ably the formula:

-0 n t ONl1 OO-NH Example 3 1O of 2.8-hydroXynaphthoyli-chloro Q-amsidnie are c.1ssolved with 1% cc. of caustic soda (34 Be), 8 cc. of Turkey red Oll and a sufiicient quantity of water to make 1 liter, and in this solution well boiled out and dried yarn is padded in the usual manner. By developingthen in a dyeing bath, neutralized with calcium carbonate and containing a diazo solution of 4.7 gr. of 4'ol1loro-3-arninobenzoyianiline in the liter, a dyestufi is obtained having probably the formula:

In this manner a yellowish red shade of a very good fastness to lzier boiling is obtained.

The same shades and fastness properties are obtained by producing the dyestuffs on he fibre by the usual printing processes.

The following table gives the shades obtained on cotton material by using other of our novel azo combinations:

Diazo compound of: Combined with 2.3-hyrlroxynaphthoyl: Shades:

3-amino-4-n1ethyl-benzoyl-3-toluidine of the formula:

NHz CH3 OH3OOO-NH 2-toluicline Fiery scarlet red D0. B-anisidine Bluish red D0. Z-phcnetidine Yellowish red D0. a-naphthylamine Bluish red D o. fl-naplitliylaniine Fiery scarlet 3-arnino-4n1ethyl-benzoyl-Z-chloroaniline of the formula:

NHz Cl CH3-C G ONIIC 2-ehlor0ani1ine Fiery scarlet Do. 2-anisldlue Clear scarlet red Do. a-naphthylamine Clear bluish red D0. finaphthylamine Fiery scarlet 3-am;no-4-metliyl-benzoyl-l-chloro-2-toluidine of the for mu a:

NHz CH3 OHaC -C O-NHQ 2-chloroaniline Fiery scarlet red C1 D0. 3-toluidine Fiery scarlet Do. 4-toluidine Fiery scarlet D0. a-naphthylamine Bluish red Do. linaphthylamme Clear red D0. Bis-(2.3-liydroxynaphthoyl) lianisidine of the formula: 7

(Two molecular proportions) 00113 /0 CH3 HO Garnet brown -o o-Nn-- -NH o 3' anglino4 methylbenzoyl-2.5-dicliloroaniline of the for- N112 Cl on; c O--NH@ Aniline Yellowish red C1 D0. rl-anigidine Yellowish red Do. a-naphtliylarnine Dark red Diazo compound of:

Combined with 2.3-hydroxynaphthoyl:

Shades:

3-amino'4-methylbenzoyl-Z-anisidine of the formula:

NHB 0 CH3 CH3C0NH 3-chloroaniline Clear bluish scarlet Do. S-nitraniline Bluisll red D0. 2-anisidine Fiery scarlet red D0. fl-naphthylamiue Fiery scarlet red 3-arg1ino-4 -1netl1ylbenzoyl-5chloro-2-anisidine of the for- NH: 0 CH CH3 C ONHC1 3-anisidine Scarlet red Do. 4-chloro2 anisidine Fiery scarlet D0. 5-chlor0-2-anisidine Fiery scarlet Do. Z-aminohydroquinone-dimethylether Orange brown Do. anaphthylamine Dark bluish red Do. B-naphthylamine Clear scarlet red Do, (Two molecular proportions) Bis-(2.3-hydroxynaphthoyl) dianisidine Garnet brown 3-aminomethylbenzoyl-4-pl1enetidine of the formula:

2-toluidine 2anisidine 4-culoro-2onisidlnc .Z-phenctidine fi-naplithylarnine Fiery scarlet Clear bluish red 'ery scarlet red Clear yellowish red Fiery scarlet 3 amino 4 methylbenzoyl uminohydroquinone di methylether of the formula:

a-naphthylamine Clear red A Do. (Two molecular proportions) Bis-(2.3-hydroxynuphthoyl)-dianisidine Garnet brown 3-amino-4-methylbenzoyl-2-aminophonylether of the formula:

2.3-hydroxynaplithoyl:

NH: 0 Calls CH; (IO-NEG B-naphthylamine Clear scarlet red 3-amino-4-methylbenzoyla-naphthylamine of the formulu:

NHz

cm-G-c ONH Aniline Clear red Dov Moluidine Clear red D0. 3-nitran iline Clear bluish red DO. 2-ams1 1h Clear yellowish red Do. 2phenet1dine Clear red D0. 2-aminoliydroquinone-dimethyletlier of the formula:

OH 0 CH3 CO-N H a Red I I 0 CH3 Do. wnaphthylamine Clear bluish red 3-amlno4-methylbenzoyl-fl-naphthylamine 0f the formula:

4 chloroaniline 5-chloro-2-toluidine 3-auisidine 4-anisidine 4-chloro-2-anisidine B-phenetidine l-phenetidine Clear red Clear red Clear red Fiery scarlet red Clear red Clear red Clear red 4- 1,e3s, 27o

Diazo ompound of: Combined with 2.3-hydroxynaphthol: Shades:

Bis-(3-amino-4-methy1benzoyl)dianisidine of the formula: Combined with two molecular proportions of:

2.3-hydroxynaphthoy1:

4-anisidine Copper brown NH; 0 CH3 0 CH N112 om-O-o ONH- NH-C 00 cm Do. B-naphthylamine Copper red Bis g aminoe -methy]benzoy1)-ortho-to1idine of the for- 5-ch1oro-2-to1uidine Red m a;

NH: CH3 CH3 NHz GHrQOO-NE- NH-ooOoH3 Do. 2-phenetidine, Yellowish red Do. a-naphthy1amine Bluish red Do. fi-naphthylamine Yellowish red We claim: 1. As new products azo dyestuifs having most probably the general formula:

O O.NH.ary1

wherein m represents a halogen atom or an alkyl group and aryl represents a residue of the benzene or naphthalene series, which dyestuffs are in the dry state reddish to dark colored powders, soluble in concentrated sulfuric acid with from blue to dark violet colors and which by reduction yield an amine of the type HEN I wherein X represents a chlorine atom or a methyl greup and aryl represents a residue of the benzene or naphthalene series, which dyestufis are in the dry state reddish to dark colored powders, soluble in concentrated sulfuric acid with from blue to dark Violet colors, and which by reduction yield an amine of the type H2N I I GO .NH.ary1

wherein X stands for a chlorine atom or a methyl group and aryl represents a residue of the benzene or naphthalene series, and an 1-amino-2-hydroxynaphthalene-3 carboxylic acid arylide, and which when produced on vegetable fibers produce reddish shades of an excellent fastness to kier boiling.

4. Vegetable fibers dyed with the dyestufl's as claimed in claim 3.

5. As new products, the azo dycstuii's of the probable general formula:

wherein It stands for a residue of: the benzene series and aryl represents a residue of the benzene or naphthalene series, which dyestuffs are in the dry state reddish to dark colored powders, soluble in concentrated sulfuric U acid with from blue to dark Violet colors, and

1 the group consisting of Cl, CH CH and which by reduction yield an amine of the with a red-violet color, and which by reductype: tion yields an amine of the formula:

(3H3 C|H3 HJN\ HzN 01 l I CO.NH.R OO.NHO

wherein R stands for a residue of the benzene series, and a 1-amino-2-hydr0xynaphthalene-i-carboxylic acid arylide, and which when produced on Vegetable fibers produce reddish shades of an excellent fastness to kier boiling.

6. Vegetable fibers dyed with the dyestuffs as claimed in claim 5.

'2'. As new products, the dyestuffs of the and 1 amino 2.3 hydroxynaphthoyl orthochloroaniline, and which when produced on vegetable fibers oroduces fiery scarlet shades of an excellent fastness to kier boiling.

10. Ve etable fibers dyed with the dye stuff as claimed in claim 9.

probable formula probable general formula: o\H3 on OO.NH o1 o11 OO.NH.R 00113 CO.NH CO.NH.ary1

which dyestuif is in the dry state a dark colored powder, soluble in concentrated sulfuric acid with a red-violet color, and which by reduction yields an amine of the formula:

wherein It stands for a phenyl residue containlngz one or two substituents selected from OC,H and aryl represents a residue of the benzene or naphthalene series, wh ch dyestuffs are in the dry state reddish to dark 1 1 1 L CH3 colored powoers, soluble 1n concentrated sul- EN I furic acid wlth from blue to dark Violet col- 2 ore, and which by reductlon yield an amine OOH of the type: 3

3 dQNH- -o1 H2N\ and 1amino-2.3-hydroXynaphthOyl-Q-aminohydroquinone-d1methylether, and which I when produced on vegetable fibers produces comma orangebrown shades of an excellent fastness to kier boiling.

12. Vegetable fibers dyed with the dyestuff as claimed in claim 11.

In testimony whereof, we affix our signatures. 1

LE'OPOLD LASKA. ARTHUR ZITSCHER.

prob able formula N=N 01 l 0 TI I CO.NHO

Conn-O which dyestuff is in the dry state a reddish powder, soluble in concentrated sulfuric acid 11. As a new product, the dyestuff of the 

